Acyclic olefin isomerization



United States Patent 3,367,988 ACYCLIC OLEFIN ISOMERIZATION John M. McEuen, Detroit, Larry Plonsker, Royal Oak, and Michael Dubeck, Birmingham, Mich., assignors to Ethyl Corporation, New York, N.Y., a corporation of Virginia No Drawing. Filed Feb. 1, 1965, Ser. No. 429,634 19 Claims. (Cl. 260-683.2)

ABSTRACT OF THE DISCLOSURE An improved process for isomerizing u-olefins to internal olefins using a Group VIII metal or metals on an inert support as a catalyst, and an alcohol as a promoter. Suitable catalysts are palladium, platinum, rhodium, iridium or ruthenium and mixtures thereof on finely divided charcoal. Paraffinic monoand dihydroxy alcohols are examples of useful promoters.

This invention relates to olefin isomerization and more particularly, to the isomerization of straight-chain terminal olefins to straight-chain internal olefins with a catalyst containing a Group VIII metal of the second or third long period of the Periodic Table, or a mixture of such metals.

Various processes for isomerizing terminal olefins to internal olefins are known in the art. However, in general, the prior art processes suffer from one or more limitations such as excessive olefin cracking, undesirable olefin polymerization, excessive randomization, or unfavorable economics. It is known that palladium and platinum halides in combination with other ingredients can be em ployed as isomerization catalysts. US. Patent 2,960,550, Nov. '15, 1960, teaches the isomerization of olefins with a catalytic medium consisting essentially of a halogenated, straight-chain, organic acid solution of a halogen-containing salt of palladium or platinum. US. 2,960,551, Nov. 15, 1960, teaches similar catalytic media which consists essentially of a phosphorus oxychloride solution of a halogen-containing palladium or platinum salt. In contrast, this invention comprises the discovery that halide salts of palladium and platinum are unnecessary, and that the isomerization of terminal olefins to internal olefins can take place in the presence of a mixture of Group VIH metals in elemental form. Furthermore, this invention comprises the discovery that halogenated reaction media such as halogenated straight-chain organic acids or phosphorus oxychloride are unnecessary in the isomerization of terminal olefins.

An object of this invention is to provide a process for the isomerization of terminal olefins to internal olefins. A more particular object is to provide a process for the isomerization of straight-chain terminal olefins to straightchain internal olefins which employs a mixture of Group VIII metals as a catalyst. A further object is to provide an isomerization process which does not entail the use of a halogenated straight-chain organic acid or phosphorus oxychloride as an integral part of a catalytic system. Additional objects will be apparent from the following detailed description and appended claims.

The objects of this invention are satisfied by a process for the isomerization of an olefin which comprises contacting an olefin with a catalytic quantity of a Group VIII metal of the second or third long period of the Periodic Table or a synergistic mixture of such metals supported on an inert matrix and a promoter quantity 3,367,988 Patented Feb. 6, 1968 of an alcohol having up to two hydroxy radicals, each of said hydroxy radicals being bonded to an organic group of from 1 to 18 carbon atoms through a carbon atom of said organic group which is bonded to at least one hydrogen atom, said organic group being acyclic and solely composed of carbon and hydrogen. In a preferred embodiment, a straight-chain terminal olefin having from 4 to 24 carbon atoms is isomerized to a straight-chain internal olefin by contacting said olefin with a catalytic quantity of a catalyst consisting of a Group VIII metal selected from the group consisting of palladium, platinum, rhodium, iridium, ruthenium, and metal mixtures of ruthenium-platinum, ruthenium-palladium, rhodium-palladium, rhodium-ruthenium, and rhodium-ruthenium-palladium, said metal or metal mixtures being dispersed on an inert support such as charcoal, and a promoter quantity of monohydric parafiinic alcohol having from 4 to 10 carbon atoms and being selected from the group consisting of primary and secondary alcohols. The metal mixtures mentioned above are highly preferred because they are synergistic.

In the process of this invention, unexpected advantages are realized. The alcohol employed (together with one or more single metal or mixed metal catalysts) unexpectedly acts as a promoter. Thus, when the above-mentioned metal catalysts are employed with an alcohol in an olefin isomerization process, the time required to attain the same amount of isomerization is decreased by a factor of from 2 to about 20 or more. Furthermore, since the alcohol promoter enhances the activity of the metal catalyst, the amount of the catalyst required per unit volume of the olefin may be decreased, as also may be decreased the temperature at which the isomerization is accomplished. Another striking eifect of the alcohol is the fact that it greatly prolongs the activity of the metal catalysts; thus the catalysts may be used for more isomerization reactions than would be possible if the metals were employed alone. Moreover, if at first a metal catalyst is used alone in the isomerization of olefins and its activity is eventually lost, mere addition of a promoter quantity of an alcohol to the reaction mixture containing the spent catalyst will immediately restore its activity, often to a higher degree than it originally possessed. This unexpected and striking promoter activity of an alcohol is of immeasurable economic value because the cost of the process of olefin isomerization may now be decreased manyfold.

The process of this invention is advantageously employed inthe conversion of straight-chain terminal'olefins having from 12 to about 24 carbon atoms to the corresponding straight-chain internal olefins. However, the process can be employed to isomerize lower olefins such as butane-1, pentene-l, heptene-l, octene-1, nonene-l, and the like. A particular feature of this invention is the high yield of ,B-olefin afforded by the process.

The reaction temperature is not critical, and conversions may be carried out at ambient temperatures or higher. However, in some instances the isomerization rate is too slow for practical use when the process is carried out at a temperature below about C. Thus, the process is generally carried out at least at C. and preferably at temperatures between about 150 C. and the decomposition temperature of the terminal olefin. A highly preferred reaction temperature is from about 150 to about 225 C. Higher temperatures, however, may also be employed with satisfactory results. Thus, higher olefins, such as dodecene-l, tetradecene-l, and hexadecene-l, may be Atmospheric pressure, or higher or lower pressures, can be employed. Atmospheric pressure is especially useful in the isomerization of olefins having from 12 to about 2 4 carbon atoms. In general, a preferred pressure range is from about 1 to about 20 atmospheres; a most preferred range being from 1 to about 5 atmospheres.

The reaction time is not a truly independent variable but is dependent at least to some extent on the other process conditions employed. In general, higher temperatures usually result in a decrease of reaction time. The reaction time is governed at least to some extent by the degree of isomerization desired. Furthermore, the reaction time depends on the amount of the catalyst used for a given volume of an olefin and on the specific metal catalyst mixture employed since some mixtures are more active than others. When carrying out the process as a batch operation, reaction times of from about min utes to about 20 hours are usually sufiicient.

In general, the alcohol which may be used in this process can be any primary or second alcohol having up to 18 carbon atoms. It is preferred, however, that the alcohol he acyclic and have about 12 carbon atoms or less and be free of carbon-to-carbon unsaturation. Although functional groups may be present in the alcohol molecule as for example chlorine, bromine, iodine or fluorine (e.g. ethylenechlorohydrin and S-bromohexan-l- 01), it is preferred that the alcohol be free of any functional groups (other than the hydroxy radical or radicals), particularly those that react with the alcohol portion and those that complex with the metal catalysts, because they have a detrimental effect on the catalytic activity. Thus, the most preferred alcohols are those which have an organic group bonded to the hydroxy radical or radicals which is composed of only carbon and hydrogen.

A'lhough carbocyclic alcohols such as cyclohexanol or phenol may be used, it is preferable to employ acyclic alcohols. Polyhydroxy alcohols such as hexylene glycol, 1,3-butanediol, and 1,4-butanediol, may be employed successful'ly in the instant process. When using a polyhydric alcohol it is preferred that the hydroxy groups should be separated by at least one carbon atom as in a l,3-diol, and more preferably, by at least two carbon atoms as in a 1,4-diol. Monohydric alcohols, however, are more preferred than polyhydric alcohols. Ethylenically unsaturated alcohols such as 2 butene-l-ol and l-heptene-4-ol-4- methyl may be used as promoters, but the best results are obtained with alcohols which are free of ethylenic unsaturation.

The preferred group of alcohols which may be advantageously employed in the process of this invention as catalyst promoters are monohydric alcohols wherein the hydroxy radical is bonded to an onganic group of from 1 to about 10 carbon atoms through a carbon atom of said group which is bonded to at least one hydrogen atom, said organic group being acyclic, solely composed of carbon and hydrogen, and free of carbon-to-carbon unsaturation. Thus, the preferred alcohols are primary or secondary parafifinic mono'hydric alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl -alcohol, allyl alcohol, n-butyl alcohol, isobutyl alcohol, secbutyl alcohol, n-amyl alcohol, isoamyl alcohol, n-hexyl alcohol, n-octyl alcohol, capryl alcohol (octanol-Z), ndecyl alcohol, lauryl alcohol, myristil alcohol, cetyl alcohol, and stearyl alcohol. Very highly preferred alcohols of the above types are the primary alcohols having from 4 to about 10 carbon atoms, and the more preferred ones are n-hexanol, n-heptanol, and n-octanol. Of these, the most preferred is n-octanol.

As mentioned above, single metals or mixtures of two or more metals, preferably in a finely divided state supported on an inert matrix, are employed as a catalyst in the process of this invention. Preferably, the supports are in finely divided form or in small states of aggregation such as pellets or tablets having a surface of sufiicient area to give an effective catalytic surface. Any inert cata- CaO Anal cine NQAISi O (H O) Chahazite 12 6 Heulandite CaAl Si O (I-I O 5 Natrolite NH Al2Sl3O10)2 CZlAl2Sl501 (H20) Thomsonite (Ca,Na )Al Si O (H O) Charcoal, and particularly finely divided charcoal, is the most highly preferred inert support.

The catalyst preferably consists of from one to about 10 weight percent of finely divided metal dispersed on an inert support of about to about 99 weight percent. It should be noted that both the metals and the inert supports can be in other states of aggregation such as pellets or tablets; but finely subdivided material is preferred because it provides larger surface area and thus increases the efficiency of the catalyst. When a catalyst is too active, however, it might be preferable to employ the metals and/ or the inert material that is in larger particle size.

The amount of catalyst employed in this process is not critical. However, it is preferred that an amount of catalyst be used which affords a reasonable amount of isomerization in a reasonable reaction time. In general, when the process of this invention is carried out as a batch operation, from about 0.01 to about 40 weight percent of a catalyst consisting of a metal mixture and an inert support is employed. A preferred range is from about one to about 15 Weight percent. Thus, for example, if 100 grams of olefin is charged to the reaction vessel, it is highly preferred that from about one to about 15 grams of a catalyst mixture, that is, a mixture of the metals and the inert support, be admixed therewith.

The amount of the alcohol as a catalyst promoter employed in the process of this invention is also not critical, but generally it should be within the range of from about 0.05 mole percent to about 50 mole percent of the olefin. The more preferred amount of the alcohol is within the range of from about 0.1 mole percent to about 10 mole percent of the olefin. It should be understood, however, that smaller or larger amounts of an alcohol may be successfully employed in this process.

The process of this invention can be carried out as a batch process or as a continuous operation. In a continuous process, an olefin, either in vapor or in liquid phase, may be contacted with the catalyst and promoter, but for practical reasons, liquid phase operations are preferred. When carrying out the process of this invention as a batch operation, it is preferred that a liquid phase be present. Thus, dodecene-l can be isomerized by refluxing a mixture of dodecene-l promoter and catalyst at atmospheric pressure. Similarly, butene-l can be isomerized in a batch operation by contacting it with a promoter and a catalyst at a pressure under which the terminal olefin is a liquid. Alternatively, butene-l (or any terminal olefin that is gaseous at the reaction temperature) can be isomerized according to the process of this invention by bubbling the gaseous olefin through a liquid reaction medium containing the promoter in contact with the catalyst.

Although this process can be conducted in the presence of a solvent, we prefer not to employ a solvent when isomerizing an alpha olefin which is in the liquid state under the reaction conditions employed.

Those solvents which may be employed should be inert under the reaction conditions. Non-aqueous material such as the saturated hydrocarbons, e.g., pentane, hexane, isopentane, dodecane, and the like are preferred, but ethers and halogenated hydrocarbons may also be used.

The processes of this invention may be carried out either in air or in an inert atmosphere. When an inert atmosphere is desired, nitrogen is preferred, mainly for economical reasons. However, other inert gases such as neon and argon may be used with equal success. When this invention is carried out as a continuous process, an inert gas, preferably nitrogen, is advantageously used as a carrier for the olefin and promoter that is being passed through the catalyst bed. In such a process, the amount of nitrogen used is measured by cubic centimeters (cc.), passed through the reaction tube per minute. It is preferred that the nitrogen flow be such that the ratio of the volume of nitrogen to the volume of olefin be from 1:1 to 100021.

In a continuous process, occasionally a single pass of an olefin through the reaction column might not yield the desired degree of isomerization. In such cases, the partially isomerized olefin may be recycled in the same manner as the fresh olefin through the reaction column to produce the desired degree of isomerization.

To appreciate the unexpectedly great advantage of the alcohol promoter in the olefin isomerization process of this invention, one need only compare the experimental conditions of identical isomerization reactions with the exception that in one example an alcohol promoter is employed and in another it is not employed. Thus, in Table 1 below are given two metal catalysts, a single metal and a mixed metal catalyst, and the results are compared when these metal catalysts are used in isomerizing dodecene-l to dodecene-Z both in the presence and in the absence of alcohol promoter. The alcohol is noctanol and it is used in the amount of one mole percent of the olefin. I

TABLE 1.ISOMERIZATION OF DODECENE-l TO 1% nil 029% Pd/C, n-

octanol.

In the above table all metal on charcoal catalysts are 5 percent by weight of metal. The above table quite clearly demonstrates that the results are startling when only one mole percent of n-octanol is used. Thus, when the single metal catalyst was used together with n-octanol as a promoter, the reaction time was decreased by a factor of almost 3 without a substantial decrease in yield. In the case of the mixed metal catalyst with n-octanol, the reaction time was decreased by a factor of over while obtaining substantially the same yield of dodecene-2. Comparison similar to the above holds true when other metal catalysts and other alcohols are employed, particularly monohydric parafiinic alcohols having one to 12 carbon atoms.

The products of this invention can be separated from the reaction mixture by any method known in the art. Suitable separation techniques include filtration, distillation, decantation, chromatography, and the like.

The following examples serve to illustrate this invention, but do not limit it. All parts are by weight unless otherwise indicated.

Example I A flask equipped with a side arm fitted with a diaphragm was charged with 18 parts of dodecene-l and 2 parts of a catalyst consisting of 9 weight percent of 5% palladium on charcoal and one weight percent of 5% ruthenium on charcoal. The flask was swept with nitrogen, one mole percent of n-octanol was added to the reaction mixture, and the contents of the flask were heated to reflux for one-half hour while stirring. The reaction mixture was then filtered to remove the catalyst and the isomerized olefin was determined by infrared and vapor phase chromatography analysis to contain 74% dodecene-2. The yield is based on the amount of reacted olefin.

When this example was repeated in the absence of n-octanol, it was necessary to reflux the reaction mixture for 11 hours to attain substantially the same degree of isomerization and substantially the same yield.

Example 2 The procedure of Example 1 was repeated using the same amount of n-octanol except that 10 weight percent of 5% palladium on charcoal was used as the metal catalyst and the reaction mixture was refluxed for two hours. The yield of dodecene-2 was found to be 71%.

When this reaction was carried out in the absence of n-octanol, the reflux time'required to obtain the same degree of isomerization and substantially the same yield was 5.5 hours.

This example was repeated following the same procedure and using the same amount of n-octanol, but replacing palladium with 10 weight percent Olf 5% iridium on charcoal. Substantially the same results as with palladium were obtained.

Example 3 Example 4 The procedure of Example 1 was repeated except that n-butanol was employed as the alcohol promoter. The yield of dodecene-Z was 79%. The use of n-butanol as the catalyst promoter resulted in decreasing the reflux time by a factor of about 20, while the yield and the degree of isomerization remained substantially the same.

Example 5 The procedure of Example 1 was repeated except that methanol was used in place of n-octanol and the reflux time was one hour. The yield of dodecene-Z was 77%. A decrease in the reflux time by a factor of about ten resulted from the use of methanol as the catalyst promoter, while the yield and the degree of isomerization remained substantially the same.

Examples 6-32 are contained in Table 2 and in all of these examples the procedure described in Example 1 was followed changing the temperature and the reaction time as indicated in the table.

In the following table, all metal on charcoal catalysts are 5 percent by Weight of metal. The weight percentages in column 3 are based on the total weight of the reaction mixture. In Examples 6 to 27 wherein mixed metal catalysts are employed, the weight percentages in column 3 show the relative amounts of each metal/charcoal component used in making up the catalyst. The ratios of the metal/charcoal components comprising the catalysts are shown in column 4, and the total amount of the mixed metal on charcoal catalyst is shown in column 5. Since the catalysts in Examples 28 to 32 are single metal cata lysts, the percentages in columns 3 and 5 are the same. In column 6 is given the amount of alcohol employed in a particular example. It is expressed in mole percent of alcohol based on the number of moles of olefin that is being isomerized.

TABLE 2 Ex. Catalyst Composition Wt. erccut M /C: Ratio of Weight Mole Tempera- Time, Product No. Olefin Wt. percent M /C an alcohol Metali: percent percent ture, hrs.

Metalz Catalyst Alcohol C.

6..- Dodecene-l 0.5% Ru/C:5% Pd/C n-octanol 1:10 5. 5 5.0 O) 4 Dodecene-Z:

1% Ru/C:5% Id/C n-octanol 1:5 6 3. 180 1 D0.

% Bil/(115% Id/C n-ootanol 1:1 1. 0 150 2 D0.

1% Ru/G:7.5% Pd/C u-octanol 1:7. 5 8. 5 1. 0 150 3 Do.

1% Rh/C:9% Pd/O n-oetanoL. 1:9 10 1. 0 150 1 Do.

1% Rh/C:9% Pd/C n-octanoL. 1:9 10 1.0 125 3 Do.

2.5% Rh/O:2.5% Ru/C n-octan 1:1 5 3.0 150 2 Do.

0.5% Rh/G:0.5% Ru/C n-octanol 1:1 1 5. 0 175 3 DO.

2% Ru/C:8% Pt/C n-oetanoL. 1:4 10 1. 0 175 4 D0.

3% Ru/C:7% Pt/C n-octanoL. 3:7 10 1. 0 175 3 Do.

5% Ru/C:5% Pt/C n-oetanol 1:1 10 1.0 175 1 Do.

0.5% Eli/010.5% Ru/O:9% Pd/C n-octanol. 10 1. 0 150 2 Do.

7.5% Ru/C:2.5% Rh/C n-nonanol 10 2.0 100 2 Tetradeeene-Z.

7.5% Ru/C:2.5% Rh/O 3-nonanol.. 10 3.0 200 1. 5 Hexacedene'2.

0.1% Ru/C:10% Rh/C 2-pentanoL-.- 10.1 2.0 45 1 Hexene-2.

0.1% Ru/C:5% Pd/G ethyl alcohol. 5. 1 10.0 65 1 Do.

3% Rh/C:7% Pd/C n-oetadecanoL. 10 1. 0 300 6 Tetraeicosene-l. Eicosene-1. 5% Rh/C;5% Pd/C n-dodeeanoL... 10 1. 0 275 3 Eicosene-2. Octadecene-L 5% Rh/G:5% Pd/G 4-dodecanol. 1O 1. 0 250 2 Octadecene-2. Decene-l 5% Rh/C:5% Ru/C n-deeanol 10 1. 0 150 1 Decene-2. 5-r1nethyldodecene- 1% Ru/C ;5% Pd/O 3-decanol. 6 3.0 150 2 5-methyldodecene-2. 2-r1nethyldodecene- 5% Ru/C :5% Pd/C 2-decan0l 10 1. 0 150 2 2-methy1dodecene-2. Dodeeene-l 10% Ru/C-n-ootanol 10 5.0 100 3 Dodecene-2.

5% Ru/C-n-hexanoL. 5 5.0 125 5 Do.

5% Rh/C-n-oetanol... 5 7. 5 125 4 Do.

10% Pt/C-n-octanol. 10 5.0 175 6 Deeene-2.

.. o 10% PtlC-n-decanol.... r 10 5.0 175 7 D0.

Examples 1, 2, 9, l3, l7, 18, 22 and 25 were repeated following the same procedure except that the metal content of the catalyst was changed from 5% metal on charcoal to 0.1%, 1%, 10%, and of a metal or metal mixture on charcoal. Results comparable to those in Table 2 were obtained.

The internal olefins produced by the process of this invention are well known compounds and have the many utilities which are known for them. For example, they are valuable chemical intermediates and can be transformed into acids by an ozonolysis reaction. Thus, for example, tetradecene-Z can be reacted with ozone to yield lauric acid, a detergent range acid. Similarly, the other internal olefins produced by this process can be ozonized to yield the corresponding acids. When ozonizing the products of the process of this invention, the reaction is generally carried out at a low temperature; e.g., from -50 to about 10 C. After the ozonization reaction is completed, the resultant reaction mixture is usually treated with another oxidant such as air or oxygen to obtain the product acid. The secondary oxidation is usually carried out at a temperature within the range of 20 to 90 C. Solvents which can be employed in the ozonolysis of olefins include inert solvents such as chloroform and carbon tetrachloride or hydroxylic solvents such as methanol and acetic acid.

Having fully described the process of this invention, the products produced thereby and their many utilities, it is desired that this invention be limited only by the lawful scope of the appended claims.

We claim:

1. A process for the isomerization of an acyclic olefin which comprises contacting said olefin with (a) a catalytic quantity of a catalyst consisting substantially of a Group VIII metal of the second and third long periods of the Periodic Table dispersed on charcoal and (b) a promoter quantity of an acyclic monohydroxy primary alcohol, said hydroxy radical being bonded to an organic group of from 1 to about 12 carbon atoms, said organic group being composed solely of carbon and hydrogen.

2. A process for the isomerization of an acyclic olefin which comprises contacting said olefin with (a) a catalytic quantity of a catalyst consisting substantially of a Group VIII metal of the second and third long periods of the Periodic Table dispersed on charcoal and (b) a promoter quantity of n-octanol.

3. A process for the isomerization of an acyclic olefin which comprises contacting said olefin with (a) a catalytic quantity of a catalyst consisting substantially of a Group VIII metal of the second and third long periods of the Periodic Table dispersed on charcoal and (b) a promoter quantity of an acyclic, monohydroxy alcohol, said hydroxy radical being bonded to an organic group of from 1 to about 12 carbon atoms, through a carbon atom of said organic group which is bonded to at least one hydrogen atom, said organic group being free from carbon-tocarbon unsaturated and solely composed of carbon and hydrogen.

4. A proces for the isomerization of an acyclic olefin which comprises contacting said olefin with (a) a catalytic quantity of a catalyst consisting substantially of a Group VIII metal of the second and third long periods of the Periodic Table dispersed on charcoal and (b) a promoter quantity of an acyclic, paraflinic monohydroxy alcohol, said hydroxy radical being bonded to an organic group of from 4 to 10 carbon atoms through a carbon atom of said organic group which is bonded to at least two hydrogen atoms, said organic group being composed solely of carbon and hydrogen.

5. A process for isomerizing a straight-chain terminal olefin having from 4 to about 24 carbon atoms to a straight-chain internal olefin, said process comprising contacting said terminal olefin at a temperature of from about 20 C. to the decomposition temperature of said olefin, with (a) a catalytic quantity of a catalyst consisting substantially of a Group VIII metal selected from the group consisting of palladium, platinum, rhodium, iridium, ruthenium, and metal mixtures of ruthenium-platinum, ruthenium-palladium, rhodium-palladium, rhodium-ruthenium, and rhodium-ruthenium-palladium, said metal being dispersed on charcoal, and (b) a promoter quantity of monohydric paraifinic alcohol having from 4 to 10 carbon atoms and being selected from the group consisting of primary and secondary alcohols.

6. The process of claim 5 wherein said temperature is between C. and 225 C.

'7. A process for isomerizing a straight-chain terminal olefin having from 12 to about 24 carbon atoms to a straight-chain ,o-olefin, said process comprising contacting said terminal olefin with a catalytic quantity of an isomerization catalyst, said catalyst consisting essentially of (a) a Group VIII metal selected from the group consisting of palladium, platinum, rhodium, iridium, ruthenium, and metal mixtures of ruthenium-platinum, ruthenium-palladium, rhodium-palladium, rhodium-ruthenium, and rhodium-rutlienium-pa'lladium, said metal being dispersed on a finely divided charcoal such that the metal content of said catalyst is from 0.1 to about 20 weight percent, and in the case of metal mixtures, such that the ratio of one metal to another is within the range of from 100:1 to 1:100, and (b) a promoter quantity of a mono hydric paratfinic alcohol having 6 to 10 carbon atoms and being selected from the group consisting of primary and secondary alcohols; said process being carried out at a temperature of from about 100 to about 300 C.

8. A process for the conversion of a straight-chain terminal olefin selected from the group consisting of dodecene-l, tetradecene-1, and hexadecene-l to a straightchain B-olefin, said process comprising contacting said terminal olefin with a catalytic quantity of an isomeriza tion catalyst, said catalyst consisting substantially of (a) from about 1 to about 15 weight percent of a Group VIII metal selected from the group consisting of palladium, platinum, rhodium, iridium, ruthenium, and metal mixtures of ruthenium-platinum, ruthenium-palladium, rhodium-palladium, and rhodium-ruthenium wherein the ratio of one metal to the other is within the range of 10:1 to 1:10, and rhodium-ruthenium-palladium wherein each metal constitutes at least 5 percent of the total metal content, said metal being dispersed on a finely divided charcoal, and (b) a promoter quantity of a primary paraflinic alcohol having from 6 to 10 carbon atoms; said process being carried out at a temperature of from about 150 to about 275 C.

9. A process for the preparation of dodecene-Z from dodecene-1, said process comprising contacting dodecene- 1 with about 10 weight percent of an isomerization catalyst consisting substantially of (a) about 5 weight percent of Group VIII metal selected from the group consisting of palladium, platinum, rhodium, iridium, ruthenium, and metal mixtures of ruthenium-platinum, ruthenium-palladium, rhodium-palladium, rhodium-ruthenium, wherein the ratio of one metal to another is within the range of 10:1 to 1:10, and rhodium-ruthenium-palladium wherein each metal constitutes at least 5 percent of the total metal content; said metal being dispersed on about 95 weight percent of a finely divided activated charcoal, and (b) a promoter quantity of n-octanol, said process being carried out at atmospheric pressure in an inert atmosphere and at a temperature within the range of from 150 C. to the reflux temperature of the system.

10. A process for the preparation of dodecene-Z from dodecene-l, said process comprising contacting dodecene- 1 with about 10 weight percent of an isomerization catalyst consisting essentially of (a) about 5 weight percent of palladium dispersed on 95 weight percent of finely divided activated charcoal, and (b) a promoter quantity of n-octanl; said process being carried out at atmospheric pressure in an inert atmosphere and at a temperature within the range of from 150 C. to the reflux temperature of the system.

11. A process for the preparation of dodecene-2 from dodecene-l, said process comprising contacting dodecene- 1 with about 10 weight percent of an isomerization catalyst consisting essentially of (a) about weight percent of ruthenium-palladium mixture, said mixture consisting substantially of one part ruthenium and 9 parts palladium dispersed on 95 weight percent of a finely divided activated charcoal, and (b) a promoter quantity of n-octanol; said process being carried out at atmospheric pressure in an inert atmosphere and at a temperature within the range of from 150 C. to the reflux temperature of the system.

12. The process of claim 1 wherein said alcohol is a monohydric, paraifinic, primary alcohol having from 1 to about 10 carbon atoms.

13. A process for isomerizing a straight-chain terminal olefin having from 4 to about 24 carbon atoms to a straight-chain internal olefin, said process comprising contacting said terminal olefin at a temperature of from about 20 C. to the decomposition temperature of said olefin, with (a) a catalytic quantity of a catalyst consisting substantially of a Group VIII metal selected from the group consisting of palladium, platinum, rhodium, iridium, ruthenium, and metal mixtures of ruthenium-platinum, ruthenium-palladium, rhodium-palladium, rhodium-ruthenium, and rhodium-ruthenhim-palladium, said metal being dispersed on charcoal, and (b) a promoter quantity of monohydric, parafiinic primary alcohol having from 1 to about 10 carbon atoms.

14. The process of claim 13 wherein said temperature is between 150 and 225 C.

115. A process for isomerizing a straight-chain terminal olefin having from 12 to about 24 carbon atoms to a straight-chain ,ti-olcfin, said process comprising contacting said terminal olefin with a catalytic quantity of an isomerization catalyst, said catalyst consisting essentially of (a) a Group VIII metal selected from the group consisting of palladium, platinum, rhodium, iridium, ruthenium, and metal mixtures of rutheniunnplatinum, ruthenium-palladium, rhodium-palladium, rhodium-ruthenium, and rhodiurn-ruthenium-palladium, said metal being dispersed on a finely divided charcoal such that the metal content of said catalyst is from 0.1 to about 20 weight percent, and in the case of metal mixtures, such that the ratio of one metal to another is within the range of from :1 to 1:100, and (b) a promoter quantity of monohydric parafiinic primary alcohol having from 1 to about 10 carbon atoms; said process being carried out at a temperature of from about 100 to about 300 C.

16. A process for the conversion of a straight-chain terminal olefin having from 12 to about 24 carbon atoms to a straight-chain c-olefin, said process comprising contacting said terminal olefin with a catalytic quantity of an isomerization catalyst, said catalyst consisting substantially of (a) from about 1 to about 15 weight percent of a Group VIII metal selected from the group consisting of palladium, platinum, rhodium, iridium, ruthenium, and metal mixtures of ruthenium-platinum, rutheniumpalladium, rhodium-palladium, and rhodium-ruthenium wherein the ratio of one metal to the other is within the range of 10:1 to 1:10, and rhodium-ruthenium-palladium wherein each metal constitutes at least 5 percent of the total metal content, said metal being dispersed on a finely divided charcoal, and (b) a promoter quantity of a monohydric paraffinic primary alcohol having from 1 to about 10 carbon atoms; said process being carried out at a temperature of from about to about 275 C.

17. The process of claim 16 wherein said straight-chain terminal olefin is selected from the group consisting of dodecene-l, tetradecene-l, and hexadecene-l.

18. The process of claim 16 wherein said alcohol is selected from the group consisting of n-butanol, n-hexanol and n-octanol.

119. The process of claim 18 wherein said alcohol is n-octanol.

References Cited UNITED STATES PATENTS 2,591,367 4/1952 McAllistcr 260-683.2 X 2,960,550 11/1960 Feller et al 260683.2 2,988,578 6/1961 Fleck et al 260-683.2 3,205,232 9/1965 Sparke et al. 260-6832 3,248,448 4/1966 Goble et a1 260683.2

OTHER REFERENCES Harrod et al., Double Bond Migration in n-Olefins Catalyzed by Group VIII Metal Complexes, Journal of the American Chemical Society, vol. 86, pp. l1761179, 1964.

DELBERT E. GANTZ, Primary Examiner.

R. SHUBERT, V. OKEEFE, Assistant Examiners. 

